CN113307809B - Graphene imide and unilateral perylene imide based on cyclooctatetraene and synthesis and application thereof - Google Patents
Graphene imide and unilateral perylene imide based on cyclooctatetraene and synthesis and application thereof Download PDFInfo
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Abstract
The invention discloses graphene imide and unilateral perylene imide based on cyclooctatetraene and synthesis and application thereof. The structural formula of the cyclooctatetraene-based graphene imide is shown as a formula 1, wherein R 1 Selected from: c 2‑60 Alkyl radical, C 1‑60 Alkoxy, C containing substituents 1‑60 Alkoxy, phenyl, substituted phenyl, alkylphenyl or substituted alkylphenyl; r 2 Selected from H, phenyl or substituted phenyl, while R 3 Is H; or R 2 And R 3 Together are phenyl or substituted phenyl, and R 2 And R 3 The attachment site of (b) is the ortho position of the benzene ring.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to graphene imide and unilateral perylene imide based on cyclooctatetraene and synthesis and application thereof.
Background
Graphene (graphene) is a polymer made of carbon atoms sp 2 The hybrid orbit forms a hexagonal two-dimensional nano material. Due to the unique pi electronic structure, stable physicochemical property and excellent photoelectric property, the compound has huge application prospect in the field of organic photoelectricity.
Imide molecules, particularly perylene bisimide (PDI), have stable physicochemical properties, a large pi-conjugated structure, strong absorption in the ultraviolet and visible wavelength range, high fluorescence quantum yield, excellent photoelectric properties, and the like. Therefore, it is widely used in the fields of organic photoconductors, organic Field Effect Transistors (OFETs), organic solar cells (OPVs), sensors (sensors), and biomaterials.
Solar energy is a renewable clean energy, and the development and utilization of the solar energy have profound significance for solving the problems of environmental pollution and energy shortage. The organic solar cell has unique characteristics of light weight, translucence, diversification, flexibility and large-scale production, and has great application in the fields of wearable energy equipment, building photovoltaic integration, photovoltaic tents, photovoltaic greenhouses and the like in the future. The synthesis of novel organic solar materials has become a hot problem of scientific research.
Therefore, the unique graphene imide rice material designed and synthesized by the invention is expected to be applied to the field of organic solar energy.
In view of the above, the present invention has been particularly proposed.
Disclosure of Invention
Based on the background technology, the invention provides graphene imide and unilateral perylene imide based on cyclooctatetraene, and synthesis and application thereof. The invention firstly uses dibromo unilateral perylene imide as a raw material to form a graphene imide compound taking cyclooctatetraene as a parent nucleus through Ullmann-type coupling reaction (Ullmann-type coupling reaction), and researches the application of the graphene imide compound in an organic photoelectric device.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a cyclooctatetraene-based graphene imide, which has a structural formula shown in formula 1:
wherein R is 1 Selected from, but not limited to: c 2-60 Alkyl radical, C 1-60 Alkoxy, C containing substituents 1-60 Alkoxy, phenyl, substituted phenyl, alkylphenyl or substituted alkylphenyl;
R 2 selected from H, phenyl or substituted phenyl, while R 3 Is H; or
R 2 And R 3 Together are phenyl or substituted phenyl, and R 2 And R 3 The attachment site of (b) is the ortho position of the benzene ring.
The above-mentioned "R 2 And R 3 Together are phenyl or substituted phenyl, and R 2 And R 3 The attachment site of (A) is ortho to the benzene ring and means R 2 And R 3 Are jointly combined into
X represents H or substituent of substituent-containing phenyl, and the substituent can be one or more than two, and the substituent position can be on benzene ring except R 2 And R 3 Any site other than the corresponding site. When X is H, the substituent is phenyl, and when X is a substituent other than H, the substituent is phenyl containing a substituent; the adjacent sites are connected with the sites of R2 and R3 in the formula 1. The formula 1 corresponding to this case is shown below:
as will be readily understood by those skilled in the art, the chemical bonds in the present invention
Represents that the chemical bond is a connecting bond; the alkyl group includes straight chain and branched chain alkyl groups.
The cyclooctatetraene-based graphene imides according to the invention, preferably, R 1 C having a substituent as defined in (1) 1-60 The substituents in the alkoxy, substituted phenyl or substituted alkylphenyl groups are selected from the group consisting of, but not limited to: c 1-60 At least one of an alkyl group, a hydroxyl group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group and a hydrazino group; more preferably, C is 1-60 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
Preferably, R 2 And/or R 3 Wherein the substituent of said substituent-containing phenyl group is selected from, but not limited to, C 1-60 An alkyl group; more preferably, said C 1-60 Alkyl is selected from, but not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.
Preferably, the alkoxy group is selected from, but not limited to: any one of methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy and eicosyloxy.
In a preferred embodiment of the present invention, the cyclooctatetraene-based graphene imide has a structural formula as follows:
wherein X is selected from C 1-60 An alkyl group; more preferably, said C 1-60 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
In the above aspect of the present invention, preferably, R 1 Selected from: c 2-60 Alkyl, phenyl or substituted phenyl; more preferably, the substituents are selected from: c 1-60 At least one of an alkyl group, a hydroxyl group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group and a hydrazino group; more preferably, C is 1-60 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
In the above aspect of the present invention, preferably, R 1 Is composed of
The second aspect of the invention provides a unilateral perylene bisimide, the structural formula of which is shown as formula 2:
wherein R is 1 Selected from: c 2-60 Alkyl radical, C 1-60 Alkoxy, C containing substituents 1-60 Alkoxy, phenyl, substituted phenyl, alkylphenyl or substituted alkylphenyl;
R 4 selected from halogen, phenyl or phenyl containing substituent. The halogen is selected from fluorine atom, chlorine atom, bromine atom or iodine atom.
According to the unilateral perylene bisimide of the invention, preferably, the C containing substituent group 1-60 The substituent of the alkoxy, the substituted phenyl or the substituted alkylphenyl is selected from the group consisting of: c 1-60 At least one of an alkyl group, a hydroxyl group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group and a hydrazino group; more preferably, C is 1-60 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
Preferably, the alkoxy group is selected from: any one of methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy and eicosyloxy.
Preferably, R 1 Selected from: c 2-60 Alkyl, phenyl or substituted phenyl; more preferably, the substituents are selected from: c 1-60 At least one of an alkyl group, a hydroxyl group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group and a hydrazino group; more preferably, said C 1-60 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
Preferably, R 1 Is composed of
Preferably, R 4 Selected from bromine atom, phenyl or phenyl containing substituent; the substituent is selected from C 1-60 An alkyl group; more preferably, said C 1-60 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
In a third aspect, the present invention provides the above method for preparing cyclooctatetraene-based graphene imide of the first aspect or the unilateral perylene imide of the second aspect, when R is 2 And R 3 Meanwhile, when the compound is H, the synthetic route is as follows:
the first synthetic route comprises the following steps:
compound 7 was subjected to Ullmann-type coupling reaction to give chemical A.
When R is 2 And R 3 When not H, the synthesis route II is as follows:
the second synthetic route comprises the following steps:
s1, carrying out bromination reaction on a compound 7 to obtain a compound 8;
s2, compound 8 and phenylboronic acid
Performing Suzuki reaction to obtain a compound 9;
s3, carrying out Ullmann coupling reaction on the compound 9 to obtain a compound 10;
and S4, performing a Schottky reaction on the compound 10 to obtain a product B.
In the second synthetic route, the compound 8 and the compound 9 are the unilateral perylene imide of the second aspect of the invention, R 4 Respectively a bromine atom and a phenyl group or a phenyl group containing a substituent. The compound 10 and the product B are the cyclooctatetraene-based graphene imide of the first aspect of the invention, and the compound 10 is R 2 Is phenyl or phenyl containing substituent, R 3 In the case of H, the product B is R 2 And R 3 Together is phenyl or substituted phenyl, and R 2 And R 3 In the case of the ortho position of the benzene ring.
Wherein the phenyl boric acid
In the compound 9, the compound 10 and the product B, X represents H or a substituent group on a benzene ring, the benzene ring can be mono-substituted, di-substituted or tri-substituted, and the substitution site can be the benzene ring except R 2 And R 3 Any site other than the corresponding site corresponds to the raw material phenylboronic acid
When X is not H, the two ortho positions of the boronic acid group are not simultaneously substituted.
Regarding the ullmann coupling reaction in the above two synthetic routes, preferably, in the synthetic route one and the synthetic route two, the ullmann coupling reaction comprises: and reacting the compound 7 or the compound 9 under the action of copper, alkali and an organic palladium catalyst to obtain a chemical A or a compound 10.
Preferably, the copper and base are in excess relative to compound 7 or compound 9, and the organopalladium catalyst is a catalytic amount. More preferably, the compound 7 or compound 9, copper, base and the organopalladium catalyst are in an equivalent ratio of: 1: (5-10): (5-10): (0.2-0.5). E.g. 1.
Preferably, the temperature of the Ullmann coupling reaction is 60-80 ℃.
The compound 7 in the synthetic route is prepared by referring to patent CN 201810750393.6.
Preferably, the copper powder is red copper powder or nano copper powder, the effect difference is not obvious in the reaction, and the reaction only needs to use common copper powder; the organic palladium catalyst comprises tetrakis (triphenylphosphine) palladium, bis (dibenzylacetone) palladium, bis (triphenylphosphine) palladium dichloride or palladium acetate, and the bis (dibenzylacetone) palladium has the best effect in the reaction; the alkali has a promoting effect on the Ullmann coupling reaction, and comprises cesium carbonate, potassium phosphate, sodium carbonate and triethylamine, wherein the inorganic alkali cesium carbonate and potassium carbonate have the best effect; the invention discloses a method for promoting copper-catalyzed Ullmann coupling reaction by using a solvent with large polarity, and the method is characterized in that N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and 1,4-dioxane are tried, wherein the dimethyl sulfoxide has the best effect.
Regarding scheme two above, preferably, the bromine source of the bromination reaction in S1 is liquid bromine, which is used in excess.
Preferably, phenylboronic acid is used in S2 because of selectivity problems
The amount of the compound is not too much, 2.5 to 3 times of the equivalent of the compound 8, and the temperature is not too high, namely 60 to 80 ℃.
Preferably, the Schottky reaction in S4 is FeCl 3 Is carried out under the action of (1). More preferably, the FeCl 3 Is used in an amount of about 100 equivalents.
A fourth aspect of the present invention provides the use of the cyclooctatetraene-based graphene imide of the first aspect or the unilateral perylene imide of the second aspect in an organic optoelectronic device.
The invention forms a tetramer of the graphene imide compound taking a series of cyclooctatetraene as a parent nucleus through Ullmann-type coupling reaction for the first time.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The conditions used in the listed preferred embodiments of the present invention are all the optimum conditions selected by condition optimization, and do not represent that the other listed conditions can not realize corresponding reactions to obtain corresponding products, but the yield is reduced.
It is noted that all numerical designations of the invention (e.g., temperature, time, concentration, weight, and the like, including ranges for each) may generally be approximations that vary (+) or (-) by increments of 0.1 or 1.0, as appropriate. All numerical designations should be understood as preceded by the term "about".
Synthesis of Compounds 7a-7 e:
the compounds 7a-7e are synthesized by replacing different raw material amines according to the synthetic route in patent CN201810750393.6, wherein R 1 Are respectively as
Example 1
This example prepares Compound Aa-Ae according to the following scheme 1
Compound Aa:
a100 mL two-necked flask was taken, 0.50g (0.759 mmol) of compound 7a,0.48g (7.59 mmol) of copper powder, 1.04g (7.59 mmol) of potassium carbonate were weighed, 20mL of dimethyl sulfoxide was put in the two-necked flask, and then the gas was purged three times, 0.35g (0.379 mmol) of bis (dibenzylacetone) palladium was added under nitrogen protection, and the mixture was heated at 80 ℃ for 48 hours. After the reaction is finished, when the system is cooled to room temperature, adding 100mL of water into the reaction system, stirring, filtering, drying, purifying by a silica gel column, and adding chloroform: petroleum ether (3:1) was used as eluent to give purple product A (76 mg) in 20% yield.
1 HNMR(400MHz,1,1,2,2-tetrachloroethane-d)δ＝8.62(s,8H),8.50(s,8H),8.39(s,8H),7.89(s,8H),5.19(s,4H),2.26(s,8H),1.95(s,8H),1.52-1.41(m,48H),0.89(s,24H).
HRMS(MALDI(N),100％):calculated(％)for C 140 H 124 N 4 O 8 :1989.9453found 1989.9457.
The Ab-Ae compounds were prepared according to the above experimental procedures by substituting 7a for 7b, 7c, 7d, and 7e, respectively.
Aa-Ae has the following structural formula:
example 2
This example prepared compound 8a, compound 9a, compound 10a and product Ba according to scheme two
Compound 8a:
a100 mL two-necked flask was taken, 1g (0.759 mmol) of the compound 7a was weighed, 30mL of chlorobenzene was weighed into the two-necked flask, 3.6g (30 eq) of liquid bromine was added thereto, and the mixture was heated at 80 ℃ for 24 hours. After the reaction, when the system is cooled to room temperature, adding sodium sulfite saturated aqueous solution into the system, stirring for 10min, stopping stirring, taking an organic layer after layering, extracting with brine, drying, spin-drying, and recrystallizing with dichloromethane and methanol to obtain black solid 8a (1.05 g) with a yield of 86%.
1 H NMR(400MHz,)δ9.75(d,J＝8.0Hz,2H),8.69(d,J＝8.0Hz,2H),7.96(s,1H),5.20(m,1H),2.29(m,2H),1.95(m,2H),1.47–1.30(m,12H),0.92(d,J＝6.6Hz,6H).
HRMS(MALDI(N),100％):calculated(％)for C 35 H 29 Br 4 NO 2 :814.8891，found 814.8891.
Compound 9a:
a100 mL two-necked flask was charged with 0.5g (0.614 mmol) of compound 8a,0.33g (1.84 mmol) of 4-tert-butylboronic acid, 30mL of tetrahydrofuran, 10mL of an aqueous potassium carbonate solution (2M), and then purged with air three times under N 2 0.036g (0.0307 mmol) of tetrakis (triphenylphosphine) palladium was added to the atmosphere and heated at 80 ℃ for 4h. After the reaction, the mixture was extracted with dichloromethane and water, and the organic phase was washed with brine, dried, spun-dried, and separated by silica gel chromatography, dichloromethane: petroleum ether (6:1) was used as eluent to give the purple product 9a (0.223 g) in 40% yield.
1 H NMR(400MHz,1,1,2,2-tetrachloroethane-d)δ＝8.10(d,J＝7.9Hz,2H),7.80(d,J＝7.7Hz,2H),7.67(s,1H),7.64–7.55(d,J＝7.7Hz 2H),7.44(d,J＝7.7Hz,2H),5.15–5.01(m,1H),2.16(m,2H),1.87(m,2H),1.42–1.19(m,12H),0.87(m,6H).
HRMS(MALDI(N),100％):calculated(％)for C 55 H 55 Br 2 NO 2 :921.2579,found 921.2594.
Compound 10a:
a100 mL two-necked flask was taken, 0.50g (0.543 mmol) of compound 9,0.35g (5.43 mmol) of copper powder, 0.750g (5.43 mmol) of potassium carbonate were weighed, 30mL of dimethyl sulfoxide was added to the two-necked flask, and then air-purging and three times of heating were carried out, 0.25g (0.271 mmol) of bis (dibenzylacetone) palladium was added under nitrogen protection, and the mixture was heated at 80 ℃ for 24 hours. After the reaction is finished, when the system is cooled to room temperature, adding 100mL of water into the reaction system, stirring, filtering, drying, purifying by a silica gel column, and adding chloroform: petroleum ether (1.
1 H NMR(400MHz,1,1,2,2-tetrachloroethane-d)δ＝8.10(d,J＝8.3Hz,8H),7.85(d,J＝8.3Hz,8H),7.78(s,8H),7.53(d,J＝7.8Hz,16H),7.25(s,16H),5.17–4.99(m,4H),2.27–2.05(m,8H),1.85(m,8H),1.46(m,72H),1.31(m,72H),0.87(q,J＝5.1,3.7Hz,24H).
HRMS(MALDI(N),100％):calculated(％)for C 220 H 220 N 4 O 8 :3047.6998,found 3047.6985.
Compound Ba:
weighing 15mg of compound 10a in a 100mL two-necked bottle, measuring 20mL of dichloromethane, and filling N into the system 2 After 30min, adding a nitromethane solution of ferric trichloride, and continuously introducing N 2 After reacting for 6 hours at room temperature, adding 10mL of methanol into a reaction bottle, extracting with dichloromethane, washing an organic phase with saline, drying, spin-drying, separating with a silica gel column, and adding petroleum ether: dichloromethane (1.5.
1 H NMR(400MHz,Chloroform-d)δ＝10.55(s,8H),10.12(s,8H),9.47(s,8H),9.07(s,8H),7.84(d,J＝8.6Hz,8H),5.50(m,4H),2.49(m,8H),2.04(s,8H),1.55–1.44(m,72H),1.43–1.13(m,72H),0.91(s,24H).HRMS(MALDI(N),100％):calculated(％)for C 220 H 204 N 4 O 8 :3031.5746,found3031.5747.
According to the above experimental process, compounds Bb-Be were prepared by replacing compounds 7a with compounds 7b, 7c, 7d, and 7e, respectively.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (16)
1. The graphene imide based on cyclooctatetraene is characterized in that the structural formula is shown as formula 1:
wherein R is 1 Selected from: c 2-60 Alkyl, phenyl, substituted phenyl or
R 2 Selected from H, phenyl or substituted phenyl, while R 3 Is H; or alternatively
R 2 And R 3 Together are phenyl or substituted phenyl, and R 2 And R 3 The connecting site of (A) is the ortho position of the benzene ring;
the substituent is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
2. The graphene imide according to claim 1, wherein the cyclooctatetraene-based graphene imide has the following structural formula:
wherein X is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
3. The graphene imide according to claim 1 or 2, wherein R is 1 Is composed of
4. The method for producing cyclooctatetraene-based graphene imide according to any one of claims 1 to 3,
when R is 2 And R 3 Meanwhile, when the compound is H, the synthetic route is as follows:
the first synthetic route comprises the following steps:
the compound 7 is subjected to Ullmann coupling reaction to obtain a chemical A;
when R is 2 And R 3 When not H, the synthesis route II is as follows:
the second synthetic route comprises the following steps:
s1, carrying out bromination reaction on a compound 7 to obtain a compound 8;
s2, compound 8 and phenylboronic acid
Performing Suzuki reaction to obtain a compound 9;
s3, carrying out Ullmann coupling reaction on the compound 9 to obtain a compound 10;
and S4, performing a Schottky reaction on the compound 10 to obtain a product B.
5. The method of claim 4, wherein in scheme one and scheme two, the Ullmann coupling reaction comprises: and reacting the compound 7 or the compound 9 under the action of copper, alkali and an organic palladium catalyst to obtain a chemical A or a compound 10.
6. The method of claim 5, wherein the copper and base are in excess relative to compound 7 or compound 9, and the organopalladium catalyst is a catalytic amount.
7. The method of claim 6, wherein the equivalent ratio of compound 7 or compound 9, copper, base, and organopalladium catalyst is: 1:10:10:0.5.
8. The process according to claim 5, wherein the temperature of the Ullmann coupling reaction is 80 ℃.
9. The method according to claim 5, wherein the organopalladium catalyst is tetrakis (triphenylphosphine) palladium, bis (dibenzylacetone) palladium, bis (triphenylphosphine) palladium dichloride, or palladium acetate.
10. The method according to claim 5, wherein the base is cesium carbonate, potassium phosphate, sodium carbonate, or triethylamine.
11. The method according to claim 5, wherein the solvent for the Ullmann's coupling reaction is N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, or 1,4-dioxane.
12. The method according to claim 4, wherein the bromine source for the bromination reaction in scheme II, S1 is liquid bromine in an excess amount.
13. The method according to claim 4, wherein the phenylboronic acid is present in S2
The molar ratio to compound 8 is (2.5-3): 1, the reaction temperature is 60-80 ℃.
14. The method of claim 4, wherein the Schottky reaction in S4 is FeCl 3 Under the action of (1).
15. The method of claim 14, wherein the FeCl is 3 The amount of (b) is 100 times equivalent to that of the compound 10.
16. Use of the cyclooctatetraene based graphene imide according to any one of claims 1 to 3 in an organic opto-electronic device.
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